Centro de Astrobiología (CSIC-INTA), Ctra. Torrejón-Ajalvir km. 4, 28850 Torrejón de Ardoz, Spain.
Chemistry. 2013 May 10;19(20):6488-97. doi: 10.1002/chem.201204313. Epub 2013 Mar 27.
The origin of nucleobases and other heterocycles is a classic question in the chemistry of the origins of life. The construction of laboratory models for the abiotic synthesis of nitrogen heterocycles in plausible natural conditions also aids the understanding and prediction of chemical species in the Solar System. Here, we report a new explanation for the origin of hydantoins, purines, and pyrimidines in eutectic water/ice/urea solutions driven by ultraviolet irradiation (in the 185-254 nm range, UVC) of acetylene under anoxic conditions. An analysis of the products indicates the synthesis of hydantoin and 5-hydroxyhydantoin, the purines uric acid, xanthine, and guanine, and the pyrimidines uracil and cytosine. The synthesis occurred together with the photo-oxidation of bases in a complex process for which possible pathways are proposed. In conclusion, an acetylene-containing atmosphere could contribute to the origin of nucleobases in the presence of a urea/water system by an HCN-independent mechanism. The presence of ice has a dual role as a favorable medium for the synthesis of nucleobases and protection against degradation and as a source of free radicals for the synthesis of highly oxidized heterocycles. A mechanism for the origin of hydantoins and uracil from urea in plausible conditions for prebiotic chemistry is also proposed.
碱基和其他杂环的起源是生命起源化学中的一个经典问题。在合理的自然条件下,通过非生物合成含氮杂环的实验室模型的构建,也有助于理解和预测太阳系中的化学物质。在这里,我们报告了在无氧条件下,紫外线(185-254nm 范围内,UVC)照射乙炔驱动下共晶水/冰/尿素溶液中尿二酮、嘌呤和嘧啶起源的新解释。对产物的分析表明,尿二酮和 5-羟基尿二酮、嘌呤尿酸、黄嘌呤和鸟嘌呤以及嘧啶尿嘧啶和胞嘧啶的合成。该合成与碱基的光氧化一起发生,提出了可能的途径。总之,在含有尿素/水体系的情况下,含乙炔的大气可以通过与 HCN 无关的机制促进碱基的起源。冰的存在具有双重作用,既是合成碱基的有利介质,又是防止降解的保护剂,也是合成高度氧化杂环的自由基来源。还提出了一种在合理的前生物化学条件下从尿素中生成尿二酮和尿嘧啶的机制。